close

Вход

Забыли?

вход по аккаунту

?

Патент USA US3038028

код для вставки
June 5, 1962
3,038,019
J. L. ROBINSON
PRIMARY CELL AND ANODE FOR USE THEREIN
Filed Nov. 3, 1958
2 Sheets-Sheet 1
EFFECT OF Al AND Zn LEVELS ON
ANODE EFFICIENCY
40H M GENERAL PURPOSE
wm,o
f.
956a 0.//o a2
%Mn 0.05
am. 062
5n/0
[N I///f
\ILNM
n/Zn0/ 5 0 1/2/.70.5
.7.
2
O
a.
0
25
3.0
% ?/uminum
l
1
EFFECT OF Al AND Zn LEVELS ON
MAXIMUM DELAYED ACTION
4 OHM GENERAL PURPOSE
0.5
I. 0
/.5
I 2.0
2.6
3.0
3.6
~
70 ?/um/num
{£92
BY
5/142.
HGEIVT
-
June 5, 1962
J. |_. ROBINSON
3,038,019
PRIMARY CELL AND ANODE FOR USE THEREIN
Filed Nov. 3, 1958
'
2 Sheets-Sheet 2
/i2
__/24
INVEN TOR.
John L. Rabin son
BYK'MQ Q. @7014)
HGENT
United States Patent 0 ” ice
1
3,038,019
PRIMARY CELL AND ANODE FOR USE THEREIN
John L. Robinson, Freeland, Mich, assignor to The Dow
Chemical Company, Midland, Mich, a corporation of
7
3,038,019
Patented June 5, 1962
2
ing between .5 percent and 2.0' percent of zinc the anode
e?iciency rises. The data ‘for alloys having both .5 per
cent Zinc and 1.0» percent zinc lie so closely along the
same line that only a single line for-alloys having these
Delaware
zinc
content values has been plotted on the graph.
Filed Nov. 3, 1958, Ser. No. 771,652
FIG. 2 shows that delayed action time is, in general,
6 Claims. (Cl. 136-83)
lower if the zinc content of the alloy is low. The 0.5
weight percent zinc line approaches zero delayed action
This invention relates to battery anodes and particu~
time when the aluminum content of the alloy is about .4
larly to magnesium alloy anode metals for use in primary
Hi weight percent. However, an anode made of such an alloy
cells.
has low efficiency in the aluminum content range where
For many years those skilled in the art of making pri
low delay time occurs.
mary cells in which a magnesium alloy has been used
What has not been realized until this invention is that
as the anode material have endeavored to increase the
e?iciency of the anode metal (get an ever larger number
a range of aluminum content (with coordinated Zinc
range) in an alloy exists in which an increase in alumi
of ampere hours output per pound of alloy), and to
shorten the delayed action time (the delay between the
num content of the alloy ‘(within limits) results in in
creased anode e?iciency and, unexpectedly, in a decrease
time the primary cell is put into a circuit and the time
in maximum delayed action time. ‘
the cell delivers an operating potential into the circuit).
The maximum delay time in seconds rather than mini
Considerable progress has been made both in increas
ing anode e?iciency and in reducing the delayed action 20 mum or average delay time in seconds is used as the ordi
nate in the graph of FIG. 2 because maximum delay time
time of magnesium anode primary cells, but further prog
ress is desired.
value gives the one set of values which de?ne the re—
In the course of research in connection with the use
of magnesium alloys as anode material in a primary cell
liable delay performance characteristics of the anodes
the zinc level in the alloy, that the delay time increased.
dividing the actual weight loss into the theoretical weight
of a particular type.
it was found that magnesium alloys containing zinc and 25 The four ohm general purpose test used in compiling
data used in the graph involved “D” size batteries dis
aluminum were preferred for such usage. It was found
that by increasing the aluminum level of the alloy to 3
charged through a four ohm resistance, 5 minutes per
day, 7 days per week, to a cut-off voltage of 1.2 volts
or 31/: weight percent thereof that anode e?iciency could
per cell. Anode e?iciency is measured by weighing the
be increased substantially. It was also believed that as
the aluminum level of the alloy increased, irrespective of 30 anode before and after the completion of the test and
loss (based on total ampere hours delivered by the cell)
times 100.
“rule of thumb,” for many years- the proposition that in
a given alloy system increased delayed action and in»
While the broad range of aluminum-zinc values which
creased anode e?iciency went hand in hand. This assump 35 de?ne the invention has been listed above, it has been
found that preferred results are obtained when the alumi
tion was based on the fact that the level of delayed ac
num content of the anode alloy is between 1.6 and 2.0
tion and the level of anode e?iciency are both believed to
In other words those skilled in the art followed, as a
weight percent, between 1.0 and 1.5 weight percent zinc,
be dependent on the surface ?lm formed on the cell
between .1 and .25 weight percent calcium, balance com
anode during usage. It was assumed that the more co
herent and impervious the ?lm formed on the anode sur 40 mercial magnesium with iron, nickel and manganese as
stated above in reciting the broad range of the alloy of the
invention. A preferred anode composition is 1.8‘ weight
would increase as a function of resistance to the break
percent aluminum, 1.3 percent zinc, .15 weight percent
down of the ?lm.
calcium, balance commercial magnesium containing not
Accordingly, a principal object of this invention is 45 more than .005 weight percent iron, .0102 Weight percent
to provide an improved magnesium anode alloy which
nickel and .01 weight percent manganese.
face, the higher would be the anode e?iciency. It was
also assumed that the delayed action time of the cell
- has inherently high anode e?iciency and low delayed
The minimum aluminum concentration was established
action characteristics.
at 1.6 weight percent, as below this concentration low
The invention, as well as additional objects and ad
anode e?'iciencies (35 percent or below) resulted. On
vantages thereof, will best be understood when the follow 50 the other hand aluminum concentrations above 2.5 weight
ing detailed description is read in connection with the
percent resulted in high delayed action. The zinc level
accompanying drawing, in which:
should be controlled to give an aluminum, zinc ratio of
FIG. 1 is a graph showing the effect of aluminum and
between 1 and 2, as discussed above, to maintain accept
zinc levels on anode e?‘iciency of a magnesium anode
able anode efficiency and low delay.
alloy;
55
The battery 10 shown in FIG. 3 illustrates a primary
FIG. 2 is a graph showing the effect of aluminum and
cell incorporating an anode 12 made in accordance with
zinc levels on maximum delayed action in magnesium
this invention. The battery 10 includes a coaxially dis
anode alloys, and
posed cathode electrode 14 within a cylindrical casing 16
FIG. 3 is a side elevational view partly in section,
which has a metal bottom 18. The anode 12, disposed
showing a primary cell having an anode in accordance 60 between the cathode electrode 14 and casing 16, is elec
with this invention.
trically connected to the bottom 18 by means of a strip
In accordance with this invention there is provided
connector 20 which is secured to both the anode and cas
a magnesium alloy anode metal comprising 1.6 percent
ing bottom. The cathode electrode 14 is insulated from
to 2.5 percent aluminum, zinc from one-half to one times
the bottom 18. A separator bag 22 ?lled with suitable
the aluminum concentration (the aluminum/zinc ratio 65 cathode mix and electrolyte 24 encases the lower part of
must be in the range of 1 to 2), up to .5 percent calcium,
the cathode electrode 14 and is disposed against the anode
the balance being commercial magnesium containing not
12.
over .005 percent iron, not over .002 percent nickel and
casing 16 with the upper part of the cathode electrode 14
extending therethrough. A vent tab 28 extends through
not over .1 percent manganese.
Above the anode a wax seal 26 extends across the
Referring to FIG. 1, it may be seen that in general as 70 the seal 26 to vent gases generated as the cell is used.
the aluminum content rises in magnesium alloys contain
Although only the above type primary cell is described
r .
3,038,019
4,
it is Gbvious that the anode of this invention may be
3. An anodermetal for use in a primary cell comprising
used in a wide variety of types of primary cells as well
71.8 weight percentof aluminum, 1.3 weight percent of
zinc, .15 weight percent of calcium, not over .005 weight
percent iron, not over .002 weight percent nickel, and
' as several types of electrolytes and'cathode mixes.
Anodes made in accordance with this invention have
been tested and show good results, for example, when usedv 5 not over .1 weight percent manganese, the remainder being
in cathode mix and bromide type electrolyte mixes as de-_
substantially. all magnesium.
,
,
_ g
,
4. A primary cell comprising at least a cathode, elec
trolyte and an anode, said anode comprising from 1.6
water as an electrolyte.
,
‘
to 2.5 weightpercent of aluminum, between .8 and 2.5
Cells used in obtaining the test data recorded on the
graphs, of the drawing were made with a cathode mix con 10 weight percent of zinc, the amount of 'Zinc in a given alloy
being between one half and one times the amount of
taining 87 percent lay-weight of manganese dioxide, 3‘
aluminum therein, between about .1 weight percent and
percent basic Zinc chromate, and 10 percent acetylene
.5 percentof calcium, not over .005 weight percent iron,
black to which wasadded 2.5 grams of powdered mag
not over .002 weight percent nickel, and not over .1
nesium per 1,000 grams of dry cathode mix. _The dry
mixture was Wetted with, 410 cubic centimeters of elec-, 15 weight percent manganese, the remainder being substan
tially all magnesium.
trolyte per 1,000 grams of dry cathode mix. The elec
5. A primary cell comprising at least a cathode, elec
trolyte contained 375 grams per liter of magnesiumbro
trolyte and an anode, said anode comprising from 1.6 to
mide, 25 grams perliter of zinc bromide and .25 gram per
2.0 weight percent of aluminum, between 1.0 and 1.5
liter of sodium chromate, the balance being water.
._ Similar resultshave, however, been achieved with other 20 weight percent of zinc, the amount of zinc in a given alloy
beingbetween one half and one times the amount of
manganese dioxide depolarized cathode mixes moistened
aluminum therein, between .1 and .25 Weight percent of
with aqueous solutions of chlorides or bromides of alkali
calcium, not over .005 weight percent iron, not over .002
earth metals.
'
weight percent nickel, and not over .1 weight percent man
scribed in US. Patent ,No. 2,547,907 and also using sea’
.
I
claim:
I
p
v
,
,
v
~
,, ,1‘, An anodemetal for use in a primary cell comprising 25
ganese, the remainder being ‘substantially all magnesium.
from 1.6 to 2.5 weight percent of aluminum, between .8
and 2.5 weight percent of zinc, the amount of Zinc in a'
6. A primary cell comprising at least a ‘cathode, elec
trolyte and an anode, said anode comprising 1.8 weight
percent of aluminum, 1.3 weight percent of zinc, .15
given alloy being between one half ‘and one times the
Weight percent of calcium, not over .005 weight percent
amount of aluminum therein, between about .1 weight
percent andv .5 weight percent of calcium, notrover .005
weight percent iron, ,notover .002weight percent nickel,
and not over .1, weight percent manganese, the remainder
being substantially all magnesium.
,
.,
,
2. An anode metal for use in a primary cell compris
ing from 1.6 to 2.0 weight percent of aluminum, between
30
iron, not over .002 weight percent nickel, and not over
._1 weight percent manganese, the remainder being sub
stantia'lly all magnesium.
'
References Cited in the ?le of this patent
UNITED STATES PATENTS
1.0,,and 1.5 Weight percent of zinc, the amount of zinc in"
2,264,309
Hanawalt __________ __
a given alloy being between one half and onetimes the
2,264,310
Hanawalt ____________ __ Dec. 2, 1941
amount of aluminum therein,‘ between .1 and .‘25 weight’
Dec. 2, 1941
2,712,564
Fry et a]. n _____ __‘__..___ July 5, 1955
percent'of calcium, not over .OOS‘Weight percent iron, not " ' 2,759,986
over .002_weight percent nickel, and not over .1 weight 110 2,836,645
Morehouse et a1 _______ __ Aug. 21, 1956
percent manganese, the remainder being substantially all
Stevens ____________ __ Apr. 26,
magnesium.
'
'
a
'
'
2,934,583
Morehouse et a1 _______ __ May 27, 1958
1960
Документ
Категория
Без категории
Просмотров
4
Размер файла
372 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа